DE4441463A1 - Low-odour compsn. for 1- or 2-component adhesives - Google Patents

Abstract

The compsn. (a) contains an activator system for radical polymerisation and a polymerisable cpd. of formula (II); CH2=CR<1>-COO-R<2>-OCO-NH-Q-NHCO2-O-R<4>a-OCO-NH-Q' -NH-COOR<4>a-O- (II); m = 0-10; R<1> = H or Me; R<2> = 2-6C alkylene or 4-21C oxyalkylene; A, Q' - 6-18C residue of aromatic, aliphatic or cycloaliphatic di-isocyanate or mixt.; R<4>a = residue of a polyester-diol with a C:O ratio of more than 2.6, a C:H ratio of less than 10 and a mol. wt. of 1000-20,000. Also claimed is a process for the prodn. of (a) by homogenising a mixt. of the components, opt. including other additives. Also claimed is an adhesive compsn. contg. activators, opt. other normal additives, and polymerisable cpds. as above.

Description

The present invention relates to a low-odor adhesive Composition based on urethane groups (Meth) acrylates and their use.

The invention further relates to a polyurethane (meth) acrylate on the Base of special polyester diols, which are also constituents may be the adhesive compositions of the invention.

Methyl methacrylate is the most commonly used monomer in commerce conventional free-radically curing reactive adhesives. Despite the good adhesive properties of these systems is their use Odor reasons increasingly limited. Also the liquid esters of acrylic or methacrylic acid with longer aromatic or Aliphatic side chains all have an intense odor and / or poor adhesion properties.

The development of low odor adhesive compositions is therefore of great interest, the composition in space temperature must be liquid or pasty.

EP-A 0 542 219 describes polyurethane (meth) acrylates on the Base of polyfunctional isocyanates and at least 8 carbons containing special atoms and in particular 2 Ethyl 3-propyl-1,5-pentanediol and / or its derivatives and their Use in combination with a radical initiator as Beschich tion, additive to inks, sealant or adhesive. The EP-A 0 542 219 further describes the combination of the polyurethane (meth) acrylates with other acrylates and methacrylates.  

WO-A-86/01153 and US-A 4,600,640 describe adhesives for Joining a thin glass plate to a thermoplastic sub strat using a solvent-free UV-curable Adhesive composition containing a (meth) acrylate monomer whose ester group contains a urethane group. Further, urethane (meth) acrylates of the general formula

CH₂ = CR'-C (= O) -O-R⁶-O-C (= O) -NH-R⁷

and polyurethane (meth) acrylates of the general formula

(CH₂ = CR'-C (= O) -O-R²-OC (= O) -NH-) _n Q

described.

R⁶ or R² is for example a methylene, ethylene or Propylene group, R 'is a methyl group or hydrogen, R⁷ or Q is an aliphatic, cycloaliphatic or aromatic group. Particularly preferred as an adhesive are 2-acryloyloxyethyl N-phenylcarbamate, 2-methacryloyloxypropyl-N-phenylcarbamate, 2- Acryloyloxypropyl-N-phenylcarbarmat and acryloyloxyethyl-N-n- butylcarbamate mentioned.

DE-A 27 27 109 describes UV-curable compositions of a mixture from a urethane group-containing monoacrylate and a Polyurethane (meth) acrylate. The hardened masses point out visibly excellent toughness properties against tropical moisture.

The polyurethane (meth) acrylates are reaction products of hydroxypropyl acrylate or methacrylate or hydroxy ethyl acrylate with hexamethylene, isophorone or toluene diisocyanate,  in the case of the monoacrylates, those with phenyl isocyanate. US Pat. No. 4,439,600 describes a composition of (A) Reaction product of a polyester diol (from adipic acid and Diethylene glycol) and an aliphatic or aromatic Diisocyanate; and (B) a comonomer which is a reaction product from an isocyanate and hydroxyethyl methacrylate (HEMA) or 2- Hydroxypropyl methacrylate or 2-hydroxypropyl acrylate. The End products show particular wetting, swelling and sticky tendencies and low volatility.

On this basis, it was an object of the present invention Low odor adhesive compositions based on urethane group-containing (meth) acrylates to provide the are liquid or pasty and their hardened masses one have particular moisture resistance (hydrolysis resistance). The adhesive compositions should also be storage stable and suitable for one- and two-component adhesive systems to be suitable and up Glass, wood, paper, metals and plastics good adhesion and have toughening properties.

The object has been achieved by a composition containing an activator system for radical polymerizations and a radical polymerizable compound of the general Formula II

[H₂C = CR¹-C (= O) -O-R²-OC (= O) -NH-Q-NH-C (= O)] ₂ [{- OR ^4a -OC (= O) -NH-Q ' - NH-C (= O)} _m -OR ^4a -O-] (II)

wherein
m = 0 to 10,
R¹ = hydrogen or a methyl group,
R 2 = a linear or branched alkyl group having 2 to 6 carbon atoms or an alkylene oxide having 4 to 21 carbon atoms,
Q and Q 'independently of one another are from 6 to 18 carbon atoms containing aromatic, aliphatic or cycloaliphatic groups derived from the basic diisocyanate or diisocyanate mixtures and
R ^{4a is derived} from a polyester diol having a C: O ratio of <2.6, a C: H ratio of <10 and a molecular weight of 1000-20000.

In addition, the composition may include one or more of the radi kalisch polymerizable compounds (A) and / or (B) of all common formula:

(H₂C = CR¹-C (= O) -O-R²-OC (= O) -NH-) _n R³ (I)

contains, in which
R¹ = hydrogen or a methyl group,
R² = a linear or branched alkyl group having 2 to 6 carbon atoms or alkylene oxides having 4 to 21 carbon atoms and
n = 1, 2 or 3,

• (A) where R3 is n = 1:
• an aryl group of 6 to 18 carbons,
• straight-chain or branched alkyl group having 1 to 18 Carbon atoms or
• - Cycloalkyl group having 3 to 12 carbon atoms;
• (B) R³ for n = 2 is: [-Q-NH-C (= O)] ₂ [{- O-R⁴-OC (= O) -NH-Q'-NH-C (= O)} _m -O-R⁴-O-] where m = 0 to 10 and
• R⁴ a) a polycaprolactone diol residue
• b) a polytetrahydrofurfuryldiol radical or
• R3 for n = 3 is: [-Q-NH-C (= O) -O- ((CH₂) ₅-C (= O)) _p -] ₃R⁵ wherein R⁵ is a triol residue of from 3 to 6 carbon atoms , linear or branched trihydric alcohol and p = 1 to 10 and

Q and Q 'independently of one another are from 6 to 18 carbon atoms containing aromatic, aliphatic or cycloaliphatic groups derived from diisocyanates or diisocyanate mixtures,
and optionally one or more (meth) acrylate comonomers (C),
the composition

• - 0-80 wt .-% of one or more of the compounds (B) and 100-20% by weight of one or more of the compounds (A) or 100-20% by weight of a mixture of one or more of Ver bonds (A) and (C), or
• - 2-80 wt .-% of one or more of the compounds (B) and  98-20% by weight of one or more of the compounds (C), respectively based on the total amount of (A) + (B) + (C).

The compounds of the formula (I) can be prepared according to the state of Technique known per se by implementing a in the Ester group of hydroxyl-containing acrylates (R¹ = H) or Methacrylates (R¹ = CH₃) with isocyanate-containing verbin to form a urethane group.

The acrylates or methacrylates are inventions according to hydroxyalkyl acrylates or methacrylates, wherein the alkyl groups can be linear or branched and between 2 and 6 Contain carbon atoms. According to the invention, the Esters of acrylic acid and methacrylic acid with polyethylene glycol and / or polypropylene glycol can be used. Such acrylates or methacrylates contain 4 to 21 carbon atoms in the ester group, corresponding to 2 to 10 ethylene oxide units and 1 to 7 Propylene oxide units. The preparation of such esters is the Specialist known.

Component (A)

Urethane (meth) acrylates of the formula (I) for n = 1 are known and can by known methods from the underlying Iso cyanates by reaction with the corresponding hydroxyl groups containing (meth) acrylates of the general formula

H₂C = CR-C (= O) -O-R-OH

to be obtained.  

Such methods are disclosed in WO-A-86/01153 or US-A 4,439,600 described.

Suitable acrylates or methacrylates are those for which R² is a Ethylene, propylene, isopropylene, n-butylene, isobutylene group or 4-7 ethylene oxide or propylene oxide units.

Preferred for the reaction of the isocyanates with the hydroxyl groups however, carrying acrylates or methacrylates become hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy propyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, polypropylene glycol acrylate and polypropylene glycol methacrylate.

For the straight-chain or branched alkyl groups having 1 to 8 Carbon atoms for R³ are in particular methyl, Ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, Pentyl, isopentyl, neopentyl or the hexyl group.

The cycloalkyl groups having 3 to 12 carbon atoms are preferably those selected from cyclopro pyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.

As aromatic groups containing 6 to 18 carbon atoms are in particular the phenyl, 2-toluenyl, 4-toluenyl and xylenyl group to be mentioned by reaction of the hydroxyl groups ent holding (meth) acrylates with the corresponding isocyanates to be led.

Component (B)

In the case of the compounds of the general formula (I) in the case where n = 2, they are reaction products of the above Hydroxyl-containing acrylates or methacrylates with iso cyanates, which are obtainable by reaction of suitable diols with diisocyanates. The diols are a) poly caprolactondiole, b) polytetrahydrofurfuryldiols and c) special ones Polyester.

The molar ratio in the reaction of the diols with the diiso Cyanates can vary in the ratio of 1: 2 up to 1: 1.1.

a) Polycaprolactonediols are known per se methods he by ring opening polymerization of caprolactone ge suitable diols, wherein the ratio of caprolactone to diol 1 to 20, that is 2 to 40 moles of caprolactone per mole of diol is set. The molecular weight of the polycaprolactone diols is between 200 and 4000.

Particularly suitable diols are linear or branched divalent, 2 to 6 carbon atoms containing alcohols out of question are selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2- or 1,6-hexanediol, 1,10-decane diol.

The reaction products of the diol and the caprolactone become closing by methods known to those skilled in the art with aromatic, reacted aliphatic or cyclic diisocyanates. suitable Diisocyanates, of which Q and independently of Q 'from are selected from 2,4-toluenediisocyanate, 2,6-toluenedi isocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-dicyclohexyl diisocyanate, meta- and para-tetramethyl-xylene-diisocyanate, 3-iso cyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (Isophorondi  isocyanate), hexamethylene diisocyanate, 1,5-naphthylene diisocyanate, Dianisidine diisocyanate, di (2-isocyanatoethyl) bicyclo [2.2.1] heptane 5-ene-2,3-dicarboxylate, 2,2,4- and 2,4,4-trimethylenehexamethylenedi isocyanate and mixtures thereof.

Subsequently, the reaction product of the diol, the capro lactone and the diisocyanate according to known methods with the Hydroxyl-containing acrylate or methacrylate to the poly urethane (meth) acrylate reacted.

b) The structure derived from Polytetrahydrofurfuryldiol Compounds (B) are in principle carried out according to the same scheme as described under a). First, polytetrahydrofurfuryldiol with one of the above under a) diisocyanates for the reaction ge introduced and the reaction product thereof with the already under a) mentioned hydroxyl-containing acrylates or methacrylates converted to the polyurethane (meth) acrylate. Regarding the procedure for the implementation of diols with diisocyanates is on the subject Man referred relevant literature. The molecular weight of the products is between 200 and 4500.

c) Through the use of the abovementioned polyurethane (meth) acrylates the general formula II based on special polyester diols be particularly good properties, especially in terms of Hydrophobization achieved. These polyurethane (meth) acrylates have a special elasticizing effect.

These polyurethane (meth) acrylates are Ver compounds of the general formula II

[H₂C = CR¹-C (= O) -O-R₂-OC (= O) -NH-Q-NH-C (= O)] ₂ [{-OR ^4a -OC (= O) -NH-Q ' - NH-C (= O)} _m -OR ^4a -O-] (II)

wherein R¹, R², Q, Q 'and m are as defined above speak.

R⁴ corresponds to polyester diol residues derived from polyester diols derived by a C: O ratio of <2.6, preferably <3.0 and a C: H ratio of <10. Further drawing These polyester diols by a molecular weight of 1000 to 20000, in particular from 1000 to 10000.

The preparation of these special polyester diols is carried out by order long-chain diols, in particular dimerdiol (hydrogenated Dimer fatty acid) having shorter-chain 4 to 8 carbon atoms the dicarboxylic acids or their anhydrides, in particular amber acid or succinic anhydride. The polyester diols can also be prepared by reaction of short-chain 4 to 8 carbon containing material atoms diols, in particular 1,6-hexanediol with long Chained fatty acids, especially dimer fatty acid mixture of dimeri fatty acids of acyclic and cyclic dicarboxylic acids with an average of 36 carbon atoms. But it can also Mixtures of long-chain diols with shorter-chain diols turned be set, in particular mixtures of hexanediol and poly ethylene glycol or from dimerdiol and diethylene glycol.

Generally preferred as diols are linear or ver branched C₂-C₄₄-alkyl diols such as ethylene glycol, 1,2- or 1,3- Propylene glycol, 1,2-, 1,3- or 1,4-butanediol, neopentyl glycol, 1,2- or 1,6-hexanediol, 1,10-decanediol, 1,12-octadecanediol. In Question but also come cyclic C₆-C₄₄-alkyl diols.

Further preferred are diols containing ether groups, as in For example, di-, tri- or tetraethylene or -Propylenglykol or their oligomeric homologues.  

Generally preferred as dicarboxylic acid are linear, or Branched C₂-C₄₄-alkyldicarboxylic acids, such as oxalic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, Azealic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedi carboxylic acid or its technical mixtures. To react with the Diols may also be unsaturated C₄-C₄₄ dicarboxylic acids, such as Maleic acid, fumaric acid, itaconic acid or aconitic acid become.

The esterification can according to known methods in the presence a catalyst in a suitable solvent at elevated Temperature under azeotropic removal of the water of reaction he consequences. The catalyst used is tin (II) octoate and as a solvent Xylene is preferred.

The polyester diols thus obtained are then treated with one of the above reacted under a) diisocyanates and then with the already mentioned under a) hydroxyl-containing acrylates or methacrylates to polyurethane (meth) acrylate implemented. One or more of these on the special polyester diols ba polyurethane (meth) acrylates may be mixed with Aktiva gates and optionally further customary additives as an adhesive composition.

In the case of the compounds of the general formula (I) in the case where n = 3, are reaction products of the above Hydroxyl-containing acrylates or methacrylates with Isocy Anaten, which are available by implementation of suitable 3 to 6 Carbon atoms, linear or branched three valent alcohols (triols) with caprolactone and subsequent Reaction with diisocyanates.  

Polycaprolactone triols are according to methods known per se by ring opening polymerization of caprolactone suitable triols, wherein the ratio of caprolactone to triol 1 to 10, ie 3 to 30 moles of caprolactone with one mole of triol be implemented.

Particularly suitable triols are those which are selected from glycerol, 1,2,4-butanetriol, trimethylolpropane (2-hydroxymethyl 2-ethyl-1,3-propanediol) and trimethylolethane (2-methyl-2-hydroxy methyl-1,3-propanediol).

The reaction products of the triol and the caprolactone become closing according to methods known in the art with the under a) reacted diisocyanates. Subsequently, the Reak tion product of the triol, caprolactone and diisocyanate ent according to known methods with the hydroxyl groups ent holding acrylate or methacrylate to the polyurethane (meth) acrylate implemented.

Component (C)

The adhesive composition may further comprise one or more acrylate or methacrylate comonomers (C). These monomers (C) are selected from allyl acrylate, allyl methacrylate, methyl acrylate, Methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 2- or 3-hydroxypropyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, benzyl meth acrylate, phenylethyl methacrylate, 2-phenoxyethyl methacrylate, Morpholinoethyl methacrylate, glycidyl methacrylate, piperidyl acrylamide, neopentyl methacrylate, cyclohexyl methacrylate, tert. Butyl methacrylate and tetrahydrofurfuryl methacrylate or mixtures from that.  

Preferably, the composition of the invention contains 10 to 70 % By weight of one or more of the compounds (B) and 90 to 30 Wt .-% of one or more of the compound (A) and / or (C) based on the total (A) + (B) + (C).

The adhesive compositions of the invention may be described as radi kalisch polymerizable one-component or multi-component systems, in particular two-component systems are used. In In both cases, however, there is a starter or activator system used, which the polymerization of olefinic un triggers saturated systems. Such activators is the Ability to be intrinsically activated by the ingress of ambient air its activation being in preferred embodiments should already occur at room temperature. Such activator systems usually consist of a starter component and a Accelerator component.

One-component adhesive systems should be stable in storage, in their Applikationsform malleable, in particular pasty to be flowable and have a pot life sufficient for processing, then but by the simple action of ambient air dimensionally stable Harden. The one-component adhesive systems must be up to Ein be kept protected from access by air.

The adhesive systems can also be used as multi-component, and be provided in particular as two-component systems. To prak The system then uses the components together mixed. The open pot life of the system can be adjusted by suitable Selection and adaptation of the main components of the activator system be regulated, so that here also the triggering of the startreak tion and thus the curing of the system under ambient conditions conditions in the air is possible. In one embodiment of the  Invention are the compositions of activator system and polymerizable components as well as in the case of air access reactive two-component system. Here is special preferably, the main components of the activator systems used separate from each other. Both components can then in general contain my ethylenically unsaturated reactive material. To Ver work only requires mixing these two separately holding components, shaping during open pot life of the system and the admission of ambient air.

The activator systems which can be used according to the invention can be used in Relation to the hardener (starter) in peroxide systems and hydrazone Divide systems.

The peroxide- or hydroperoxide-initiated curing of unsaturated, polymerizable systems requires especially selected Starter or activator systems when the reaction is triggered lower temperatures, for example at room temperature or only to be slightly elevated temperatures. It is known, for example example, that selected tertiary amine compounds with partial aromatic substitution on the nitrogen atom such an activator or acceleration function. Well-known activators for the Polymerisation initiation, for example by means of dibenzoyl peroxide are especially dimethylaniline and dimethyl-p-toluidine.

In the context of the invention usable peroxides are in particular Diaryl peroxides, hydroperoxides, peracids and peresters as above preferably di-tert-butyl peroxide, dibenzoyl peroxide, cumene hydro peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl hydroperoxide, Peroxiacetic acid, peroxibenzoic acid, azoisobutyronitrile or tert-butyl peracetate.

The second component of the activator of the system is selected  from tertiary amines and especially dimethylaniline and dimethyl paratoluidine, which in particular for the polymerization by dibenzoyl peroxide are particularly preferred accelerators.

As an accelerator in combination with peroxides can also heavy metal salts or their solutions are used, wherein in addition to co- in particular copper (II) salts (eg copper (II) naphthenate) are worth.

In the context of the invention, it is also possible to use hydrazones as starters or Main component in activator systems for the curing of unge saturated compounds are used by means of ambient air. The Hydrazone compounds are preferably at least in the system partially soluble metal compounds for acceleration set.

The hydrazone components preferably used according to the invention are ent speak the following general formula III

R⁵R⁶C = N-NH-R⁷ (III)

In this embodiment, the radicals R⁵, R⁶ and R⁷ have from this general formula (III) has the following meaning:

R⁵ is a straight-chain, branched or cyclic and given if substituted alkyl or optionally substi tuierter aryl radical.

R⁶ may be the same or different in importance from that R⁵ is hydrogen, a straight-chain, branched one or cyclic and optionally substituted alkyl radical or an optionally substituted aryl radical.  

In a particular embodiment, the radicals R⁵ and R⁶ can also together with the common substituted C atom a cyclo form aliphatic radical, which may also be substituted.

The radical R⁷ is again a straight-chain, branched or cyc lischer and optionally substituted alkyl or ge optionally substituted aryl radical.

The radicals R⁵, R⁶ and R⁷ can in total or at least proportion be the same, but each of these radicals can also be from the distinguish between the two other residues in its structure. As alkyl radicals are in particular straight-chain and / or branched alkyl radicals having up to 40 carbon atoms, preferably up to about 20 carbon atoms, into consideration. Cyclic residues are determined in their minimum carbons substance number by the stability of the respective ring system. A preferred lower limit here is 5 and in particular 6 C-atoms.

The radicals R⁵, R⁶ and R⁷ can be unsubstituted or substituted his. It has to be considered here that by substitution of this Remains and in particular the rest R⁷ a certain influence on the Reactivity of the activator system can be taken. Is enclosed For example, as the radical R⁷ an aromatic system, in particular a Phenyl radical, so may by suitable substitution of this Phenylrestes a reaction acceleration can be achieved by that known per se electron-donating substituents on this Phenyl radical can be provided in R⁷.

Electron-pushing and thus reaction-accelerating Substi Examples of tuents are alkyl, alkoxy and / or halogen Substituents on the phenyl radical in R⁷, on the contrary, have a strong elec ring-withdrawing substituents of the type of -NO₂ group ver  slowly on the reaction process. To such electrons shifting or electron-withdrawing effects by substitution and the structure of the respective substituents is extensive general expertise referred to here.

For more details and in particular with regard to Her position of these hydrazones, reference is made to WO-A-91/10687.

Furthermore, hydrazones of the following general formula

Ph (-C (R⁸) = N-NHR⁹) _q

be used
in which
q is a number from 1 to 3
R⁸ is H or an alkyl group of up to 40 carbon atoms and
R⁹ is independently of the other substituents H or an aromatic or aliphatic group having up to 40 carbon atoms.

These hydrazone compounds are mono-, di- or trifunctional. The radicals R⁸ and R⁹ are preferably linear and / or cyclic Alkyl groups having up to 40 carbon atoms, in particular from 3 to 8 C-atoms. At least one R⁹ residue per molecule should be one Be alkyl group. The radicals R⁸ and R⁹ can be unsubstituted or be substituted. It should be taken into account here that through the Substitution of these radicals, in particular of the radical R⁹, a some influence on the reactivity of the activator system taken can be. If, for example, an aromatic system, ins particular a phenyl radical, so may by suitable substitution This phenyl radical achieves a reaction acceleration thereby  be that known per se electron-donating substituents this phenyl radical can be provided in R⁹.

Electron-pushing and thus reaction-accelerating substituent are, for example, alkyl, alkoxy and / or halogen substituents tuenten on the phenyl radical in R⁹. Conversely, strong electrons act pulling substituents of the type of -NO₂ group slowing down on the reaction process. To such electron-pushing or electron-withdrawing effects through substitution and structure the respective substituents are extensive general Expertise referred to here.

Also, the radical R⁸ from the general formula can be selected by choosing respective constitution and any sub-items provided institution influencing the speed of the reaction process Effect.

To extraordinary diversity for the particular Be Creation of the radicals R⁸ and R⁹ from the compounds of all Common formula is the US-PS 4 010 152 with their formula images from columns 6 to 14 information. Shown here are the Hydrazone compounds already in the form of their hydroperoxides, as they also according to the invention in the reaction process in situ in access of atmospheric oxygen. The extensive details of this last referred to the specific nature of the Hydrazone compounds or the resulting from them in situ Hydroperoxides are considered to be related to the teachings of the invention with the definition of the compounds of the general formula. Out Appropriateness reasons will be made to this detailed document Liche representation in connection with the description of the invention Referenced. Of course, the benzene ring can still contain additional substituents, if they have the starter function do not bother.  

Specific examples are: acetophenone-methylhydrazone (q = 1, R⁸ = R⁹ = CH₃), acetophenone-t-butylhydrazone (q = 1, R⁸ = CH₃, R⁹ = C (CH₃) ₃).

For more details and in particular with regard to Her position of these hydrazones, reference is made to WO-A-93/01218. The at least partially soluble in the system metal compounds are characterized by the fact that especially metal compounds such Metals are used in several valence states can occur. Particularly active here are selected representatives be the transition metals. The respective selection of the metal can including rate-limiting character to Polymeri tion triggering. Highly active at room temperature Kompo nents are derived, for As of copper, cobalt, vanadium and / or Manganese off. Links of the iron comes however a special one Importance and good reaction acceleration too.

For the particularly advantageous for many applications work At room temperature, in particular iron, cobalt and / or or manganese compounds, optionally in admixture with others metallic components such as compounds of lead, cerium, calcium, Barium, zinc and / or zirconium. It can be here on the relevant Reference literature be referenced, for example, the cited publication in "Ullmann Encyklopadie der technischen Chemie ", 4th Edition, Volume 23 (1983), pages 421 to 424 and the there quoted literature.

The metals affected here are in the form of such compounds used that they at least partially soluble in the overall system are. There are both soap-like metal compounds as also in another form in particular complex to organic radicals ge related types. Typical examples of working in the  The sense of the action according to the invention is the use correspond the metal naphthenates or metal acetylacetonates. Is there a way reaching solubility of inorganic salts in the system, then is but also the use of such inorganic systems possible. A typical example of this is the iron chloride, the when used in the system according to the invention a clearly be accelerating effect shows.

It may be expedient to use the metal compounds in each case in a low valence state of the metal-for example, as cobalt (II) or manganese (II). In other cases, the use of the metal compound in the higher valence state of the metal is also suitable. For example, iron can also be used in the form of Fe ³⁺ compounds.

Reducing agents with accelerator effect can, if desired be used as activator component. These are in customary redox systems used for polymerization initiation. Reference is made to the relevant extensive literature, for example, W. Kern, Makromol. Chem. 1, 249 (1947) and C. Srna, Angew. Makromol. Chem. 9, 165 (1969) and the general Expertise, as it is z. B. is described in Houben Weyl "methods of Organic Chemistry "Vol. 14/1, 263 to 297.

Particularly active here is the class of alpha-hydroxy ketones, for example with their representatives butyroin, benzoin or Azetoin proved. It is essential that this class of substances in the Although an important in accordance with the invention used activator systems reaction-accelerating function can take over, however their co-use is not mandatory.

Starter or activator systems from the main described here  components hydrazone compound, at least partially soluble metallic drier and / or optionally used Accelerators can replace the peroxidic starter systems be used.

In the compositions of the invention, the peroxide and Hydrazone activator mixtures preferably not more than about 15% by weight and in particular not more than about 10% by weight, based in each case on the whole system. Depending on the activity of the compo used The weight of the activator mixture can be very high be lowered and, for example, to the range of about 0.1 Wt .-% or at least about 0.5 wt .-% can be reduced. Especially quantities of the activator system of at least about 1 may be suitable % By weight preferably up to about 8% by weight.

The three aforementioned components of the hydrazone activator system can preferably be used in the following proportions:
Hydrazone compounds: at least about 0.1% by weight, preferably from 0.5 to 7.5% by weight, preferably from 1 to 4% by weight of metal of soluble metal compound: from 0 to a few% by weight, conveniently about 50 ppm to 1 wt .-%, preferably more than 100 ppm, z. B. 1000 to 5000 ppm. Reducing agent: 0 to 5 wt .-%, preferably 1 to 3 wt .-%, each based on the total mixture.

To control the reaction process and / or the open pot life can inhibitors and / or Stabili in a conventional manner against premature initiation of the radical reaction be used. Their quantity is measured according to the specified Purpose. It can in individual cases by professional considerations and / or easily determined by preliminary tests. The with  used stabilizers are usually few percent - z. B. about 2 to 5 wt .-% - of the total mixture and are generally below 1 wt .-%, based on the Total mixture.

The invention in each case allows the compilation of optimized Adhesive compositions. While maintaining the inventive Laws may include soluble and / or insoluble fillers, Elastification agents, thickeners, thixotropic agents, Pigments, adhesion promoters, stabilizers and the like with can be used without the functionality of the invention according to the composition is endangered. Prerequisite is of course, that by selecting the excipients and fillers safely disturbances in the interaction of the activator components excluded. For this general chemical knowledge applies.

To inhibit the systems according to the invention are in itself known manner several mechanisms available. Mentioned the following two basic types:

• 1. stabilization against O₂, addition of antioxidants and
• 2. Stabilization against radicals, addition of radical inhibitors.

From the general chemical knowledge in the following typical stabilizer components are enumerated, wherein in each case in parentheses behind the special compound is indicated to which mechanism the stabilizer is assigned:
Pyrogallol (1), O₂-inhibited acrylates (1), hydroquinone (1,2), hydroquinone monomethyl ether (1,2), butylated hydroxytoluene (2) and phenothiazine (2). Particular importance for stabilizing the system against undesired premature Abreaktion can come compounds of the type of triphenylphosphine and NaI and I₂.

The composition according to the invention can be used as aerobically curing Adhesive system, brushable agent for surface treatment Stratification with polymerizable in particular solvent-free Paints and varnishes in the spirit of spreadable air drying paint systems, for the production of moldings under Reaction release by the action of ambient air, for example wise based on styrene / unsaturated polyester resins and as Sealant and used in printing inks.

For the preparation of the adhesive compositions according to the invention For example, the radically polymerizable compound or the Ver bonds with the activator system and optionally further Additives in the desired proportions in a stirring apparatus homo genisiert. For one-part adhesive compositions is on it to ensure that the homogenization to the exclusion of air takes place. For this purpose, it has proved to be useful, the Stirring apparatus with the polymerizable compounds before addition the last activator component (with hardener accelerator combination to evacuate and then aerate with nitrogen. This If necessary, the procedure can be repeated several times.

For the preparation of the two-component systems, these precautions not mandatory. Here is the hardener and accelerator be standing activator system until the actual application of the Adhesive composition mixed so that the one component of Activator system alone or in admixture with the polymerizable Compound to the other part of the polymerizable compound ge which contains the second component of the activator system.

The compositions according to the invention are odorless, elastic fizierend, liquid or pasty and their hardened masses show good moisture resistance. Furthermore, they may problem  be formulated as a one- or two-component system and indicate glass, ceramics, metals, plastics and cellulose containing materials such as wood or paper a superb Adhesion on. This is reflected in particular by the determined Tensile shear strengths on iron sheets according to DIN 53281 (production the test specimen) and DIN 52283 (determination of tensile shear strength). However, the following examples illustrate the invention without them to restrict.

Examples I) Urethane (meth) acrylates and their preparation Example 1 (Preparation of the monomer)

1.05 mol of hydroxypropyl acrylate is stirred at 55 ° C under N₂ and added in portions with a total of 1 mole of phenyl isocyanate. The Addition takes place in such a way that the reaction temperature does not exceed 80.degree below. After complete addition, continue for 1 hour at 70 ° C on touched. Thereafter, no free NCO is detectable. The product has a viscosity of 1000 mPas.

It is stabilized with 100 ppm hydroquinone monomethyl ether. Of Further, the following urethane (meth) acrylates were prepared from following starting compounds prepared:  

Table 1

Example 2 (Use as an adhesive)

Two-component adhesive mixtures with dibenzoyl peroxide and tertiary amine starter and methacryloyloxyethyl phosphate as Adhesive give on blasted iron sheets Zugscher strength by 15 N / mm². By addition of with hardening elasticizing additives (eg methacrylate-terminated polyethers polyurethane), the strength can be over 20 N / mm² increase. A similar mixture based on MMA shows train shear strengths of 26 N / mm².

A two-component adhesive was produced:

Component a Monomer from Example 1 50 parts dibenzoyl 0.42 parts

Component b Monomer from Example 1 50 parts N, N-dimethyl toluidine 0.21 parts.

Components a and b are mixed in the ratio 1: 1 and with 1 part Methacryloyloxyethylphosphate (adhesion promoter) added. The Tensile shear strengths on sandblasted iron sheets (DIN 52283) were measured after 1 day (Table 2).  

With acetophenone-tert-butylhydrazone (APtBH) as hydrazone can with N-phenyl-methacryloyl-ethylcarbamate and N-phenyl-acryloyl-ethyl Carbamate iron bonds (5 minutes open time) with tensile shear strengths of 5-10 N / mm² are produced.

Example 3

Instead of monomer 1 was in the two-component formulation of Example 2 is a mixture of monomer 1 and the product of the reaction Hydroxyethyl acrylate and phenyl isocyanate (Table 1, a)) used.

Example 4

Instead of monomer 1 was in the two-component formulation of Example 2 is a mixture of monomer 1 and a methacrylate minuted poly-THF 2000 composition: HEMA - TDI - PolyTHF 2000 - TDI - HEMA (HEMA = hydroxyethyl methacrylate) in the ratio 8: 2 used.

example Tensile shear strength iron / iron (N / mm²) 2 15.2 3 16.1 4 20.2

II) Preparation of the polyester diols Example 5

446.6 g of dimerdiol (hydrogenated dimer fatty acid) and 60 g of succinic anhydride are heated with 50 g of xylene and 0.5 g of Sn (II) octoate for 7 hours at 185 ° C on a water. Subsequently, the xylene is distilled off in a water jet vacuum, the bath temperature is increased up to 210 ° C. The product thus obtained has an acid number (SZ) of 0.9 and an OH number (OHN) of 47, which corresponds to an average molecular weight of 2,400.
Content: 78.53% C 12.08% H 9.39% OC: O = 8.36; C: H = 6.5

Example 6

446.6 g of dimerdiol, 70 g of succinic anhydride and 0.5 g of Sn (II) octoate are reacted analogously to Example 5. The resulting poly esterdiol has an SZ of 1.7, an OH number of 25 and an average molecular weight of 4500.
Content: 78.19% C 11.92% H 9.89% OC: O = 7.9; C: H = 6.56

Example 7

97.5 g of hexanediol and 400.7 g of dimer fatty acid VD 288 are heated with 100 g of xylene and 0.5 g of Sn (II) octoate for 7 h at 195 ° C on a water. Subsequently, the xylene is distilled off, the resul animal polyester diol has an SZ of 0.1 an OHN of 19.1 and an average molecular weight of 5900 on.
Content: 77.62% C 12.15% H 10.23% OC: O = 7.6; C: H = 6.4

Example 8

97.5 g of 1,6-hexanediol and 343.5 g of dimer fatty acid are reacted analogously to Example 7. The polyester diol has an SZ of 0.3, an OH number of 55, and an average molecular weight of 2,000.
Content: 76.99% C 12.14% H 10.88% OC: O = 7.08; C: H = 6.34

Example 9

118.2 g of hexanediol, 626 g of polyethylene glycol (MW 600) and 858 g of dimer fatty acid are reacted analogously to Examples 7 and 8. The polyesterdiol has an SZ of 1.2, an OHN of 37 and an average molecular weight of 3000.
Content: 68.5% C 10.78% H 20.73% OC: O = 3.3; C: H = 6.35

Example 10

446.6 g of dimerdiol, 84.9 g of diethylene glycol, 140.1 g of succinic anhydride and 0.7 g of Sn (II) octoate are reacted analogously to Examples 5 and 6. The resulting polyester diol has an SZ of 2.0, an OH number of 31 and an average molecular weight of 3200.
Content: 71.94% C 10.73% H 17.33% OC: O = 4.15; C: H = 6.7

Example 11

718 g (1.33 mol) of dimerdiol, 570 g (1 mol) of dimer fatty acid and 0.6 g of Sn (II) octoate are heated to 150 ° C. Within 6 hours, the temperature is raised to 225 ° C with a vacuum of 1.333 kPa (100 torr) applied from the 2nd hour. After 6 hours, the mixture is heated to 240 ° C. for an additional 8 hours in an oil pump vacuum. After completion of the reaction, the polyester diol obtained has an acid number of 0.5, an OH number of 31 and an average molecular weight of 36,000.
Content: 81.2% C, 12.77% H 6% OC: O = 13.5; C: H = 6.36

III) Preparation of Polyurethane Methacrylates (PUMA) General manufacturing instructions

0.2 mol of the polyester diol are heated to 45 ° C. To do this  within 5 min. 0.4 mol Desmodur T 100 (2,4-toluene diisocyanate (TDI), commercial product of the company Bayer, Leverkusen), where the temperature is kept at a maximum of 55 ° C. There will be another 15 minute heated to 55-60 ° C until the NCO content of the mixture 50% of Output value has reached. Then, 0.2 mol of hydroxypropyl methacrylate (HPMA) was added and the mixture heated to 80 ° C until the NCO content has fallen below 0.1%. It results in an 80% Solution of PUMA in excess HPMA.

Comparative Example 12

It is a polyurethane methacrylate (PUMA) with CAPA 220 (Polycapro lactone, commercial product of Interox, 62.4% C; 8.86% H; 28.72 % O; C: O = 2.17; C: H = 7.05) according to the above general preparation instructions synthesized.

IV) Adhesive formulations a) General manufacturing instructions for two-component adhesive stofformulierungen Type I

Component A: 37.5 parts by weight of methacrylate monomer, 62.5 parts by weight PUMA (prepared according to the corresponding examples), 0.5% by weight Parts JPA 514 (adhesion promoter: methacryloyloxyethyl phosphate, Commercial product of Johoku Chem.) And 1 part by weight of N, N Dihydroxyethyl-p-toluidine homo by vigorous stirring genisiert.

Component B: Benzoyl peroxide 20% on gypsum.

The adhesive is made by mixing 4 parts by weight of Component A.  and 1 part by weight of component B for curing.

Type II

Component A: 37.5 parts by weight of methacrylate monomer, 62.5 parts by weight PUMA and 3% Trigonox K80 (cumene hydroperoxide, 80% solution in Cumol, commercial product from Akzo) are stirred vigorously homogenized.

Component B: 37.5 parts by weight HPMA, 62.5 parts by weight PUMA, 1 part by weight Part JPA and 1 part by weight 8% copper (II) naphthenate solution (Soligen copper, commercial product of Borchers) are by Stirring homogenized.

The glue is made by mixing equal volumes of the components A and B hardened.

b) General preparation instructions for one-component reaction adhesives Type III

37.5 parts by weight of methacrylate monomer, 62.5 parts by weight of PUMA, 0.5 Parts by weight of JPA 514, 1 part by weight of iron (III) acetylacetonate and 0.1 Parts by weight of sodium iodide are homogeni in a stirred apparatus siert, evacuated and then aerated with nitrogen. To the complete exclusion of oxygen, this process is still twice repeated. Then in the nitrogen countercurrent 3 parts by weight Acetophenone tert-butylhydrazone added and the mixture again evacuated with stirring and aerated with nitrogen.

For curing or gluing the adhesive is applied to the parts to be joined applied (2.4 g / m²), exposed to ambient air for 5 minutes and then the parts to be glued joined and fixed.  

Type IV

Procedure and components analogous to type III, only becomes aceto phenone-methylhydrazone instead of the corresponding tert-butyl Hydrazons used.

The tensile shear strengths are in accordance with DIN 53283 s.einschnittig overlapped (250 mm²) samples performed. The moisture resistance is determined by measuring the tensile shear strength after a climatic storage the cured bond of 10 days at 40 ° C and 99% rela tiver humidity. The peel strengths are decreasing DIN 53282 determined at plate angles after 72 h storage at RT.

The results of the tensile shear test with and without climate storage and the angle peel tests are in the following Table 3 shows:  

Table 3

V) Preparation of an adhesive composition from a poly urethane methacrylate mixture based on polycaprolactone diol and triol reactants

540 g (1 mol) of polycaprolactone triol, MW 540 (CAPA 305, commercial product from Solvay)
1376 g (0.65 mol) of polycaprolactonediol, MW 2000 (CAPA 220, commercial product from Solvay)
748 g (4.3 mol) of 2,4-toluene diisocyanate (Desmodur T 100, commercial product of Bayer)
1430 g (9.9 mol) of hydroxypropyl methacrylate (HPMA 97, commercial product of Röhm)
1.23 g of hydroquinone monomethyl ether (commercial product from Fluka)

Preparation Method

The polyols are placed in a stirring apparatus and at 50 ° C. heated. The toluene diisocyanate (TDI) is removed within 30 min. added dropwise, the temperature of the mixture does not exceed 55 ° C increases. After completion of the addition is for 45 min. heated to 60 ° C, until the NCO content has reached a value of 6.8%. It will be the Hydroquinone monomethyl ether and the HPMA are added and the mixture while heated to 80 ° C until the NCO content is <0.1%. It is in the reaction product to an 80% solution of Polyurethane (meth) acrylates in (excess) HPMA.

VI. Composition based on polyurethane (meth) acrylate in a mixture with another acrylate or methacrylate comonomer basic formulation monomer

20% PUMA (From PolyTHF, MDI, HEMA)
3% acetone-phenyl-hydrazone (APH)
1.3% Fe acetylacetonate
2% butyroin
0.5% HEMA phosphate
Triphenylphosphine (TPP, 5 mol% based on APH).

In this basic recipe, the in the following tables were added introduced monomers and used with the resulting adhesives Iron bonding performed.

Table 4

Table 5

The tensile shear strength of the overlapping bonds (adhesive surface 250 mm²) was determined according to DIN 53283. Both One-component systems were used for joining parts with the adhesive painted and for a defined time (1 min, 5 min, in some 20 minutes) left open and then joined. The Initial strength (fixture time) is the time after joining, in the bond holds an attached weight (about 3 kg). The final strengths were at one-component and at Two-component systems 24 hours after bonding to one Zwick tensile machine determined.

Claims (15)

1. A composition comprising an activator system for free-radical polymerizations and a free-radical polymerizable compound of general formula II [H₂C = CR¹-C (= O) -O-R²-OC (= O) -NH-Q-NH-C (= O)] ₂ [{- OR ^4a -OC (= O) -NH-Q'-NH-C (= O)} _m -OR ^4a -O-] (II) wherein
m = 0 to 10,
R¹ = hydrogen or a methyl group,
R 2 = a linear or branched alkyl group having 2 to 6 carbon atoms or an alkylene oxide having 4 to 21 carbon atoms,
Q and Q 'independently of one another are aromatic, aliphatic or cycloaliphatic groups containing from 6 to 18 carbon atoms, which are derived from the basic diisocyanate or diisocyanate mixtures and
R ^{4a is derived} from a polyester diol having a C: O ratio of <2.6, a C: H ratio of <10 and a molecular weight of 1000-20000. 2. Composition according to claim 1, characterized in that the composition additionally one or more of the radically polymerizable compounds (A) and / or (B) of the general formula: (H₂C = CR¹-C (= O) -O-R²-OC (= O) -NH-) _n R³ (I), wherein
R¹ = hydrogen or a methyl group
R² = a linear or branched alkyl group having 2 to 6 carbon atoms or alkylene oxides having 4 to 21 carbon atoms and
n = 1, 2 or 3,

• (A) where R3 is n = 1:
• an aryl group of 6 to 18 carbons,
• a straight-chain or branched alkyl group having 1 to 18 carbon atoms or
• a cycloalkyl group of 3 to 12 carbon atoms;
• (B) R³ for n = 2 is: [-Q-NH-C (= O)] ₂ [{- O-R⁴-OC (= O) -NH-Q'-NH-C (= O)} _m -O-R⁴-O-] where m = 0 to 10,
• R⁴ a) a polycaprolactone diol radical,
• b) a polytetrahydrofurfuryldiol radical or

R3 for n = 3 is: [-Q-NH-C (= O) -O- ((CH₂) ₅-C (= O)) _p -] ₃R⁵ wherein R⁵ is a triol residue of from 3 to 6 carbon atoms , linear or branched trihydric alcohol and p is 1 to 10 and
Q and Q 'independently of one another are aromatic, aliphatic or cycloaliphatic groups containing from 6 to 18 carbon atoms, which are derived from diisocyanates or diisocyanate mixtures,
and optionally one or more (meth) acrylate comonomers (C),
the composition

• - 0-80 wt .-% of one or more of the compounds (B) and 100-20 wt .-% of one or more of the compounds (A) or 100-20 wt .-% of a mixture of one or more of the compounds Ver (A ) and (C), or
• 2-80% by weight of one or more of the compounds (B) and 98-20% by weight of one or more of the compounds (C), in each case based on the total amount of (A) + (B) + (C), contains.

3. Composition according to claim 2, characterized in that it

• 10-70% by weight of one or more of the compounds (B) and 90-30% by weight of one or more of the compounds (A) and / or (C), in each case based on the total amount of (A) + (B ) + (C).

4. Composition according to claim 1, 2 or 3, characterized characterized in that R² is selected from ethylene, propylene, i-propylene, n-butylene, i-butylene, ethylene oxide or Propylene oxide units.   5. Composition according to one or more of claims 2 to 4, characterized in that for n = 1 R³ is selected from Methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, Pentyl, hexyl, phenyl, xylyl, tolyl, cyclopropyl, Cyclobutyl, cyclopentyl and cyclohexyl groups. 6. Composition according to one or more of claims 1 to 5, characterized in that Q and Q 'independently derived from diisocyanates selected from 2,4-toluenedi isocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-dicyclohexyl diisocyanate, meta- and para-tetramethyl xylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), hexamethylene diisocyanate, 1,5- Naphthylene diisocyanate, dianisidine diisocyanate, Di (2-isocyanatoethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate, 2,2,4- and 2,4,4-trimethylene hexamethylene diisocyanate and mixtures it. 7. Composition according to one or more of claims 2 to 6, characterized in that the (meth) acrylate comonomer (C) consists of is selected from allyl acrylate, allyl methacrylate, methyl acrylate, Methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 2- or 3-hydroxypropyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, benzyl meth acrylate, phenylethyl methacrylate, 2-phenoxyethyl methacrylate, Morpholinoethyl methacrylate, glycidyl methacrylate, piperidylacryl amide, neopentyl methacrylate, cyclohexyl methacrylate, tert-butyl methacrylate and tetrahydrofurfuryl methacrylate or mixtures thereof. 8. Composition according to one or more of claims 1 to 7, characterized in that the activator system is a peroxide Activator system is.   9. Composition according to one or more of claims 1 to 8, characterized in that it as a one-component system or as Two-component system is present. 10. A process for the preparation of the composition as in Claims 1 to 9 defined by homogenization of the poly merisierbaren compound or compounds, the activator systems and, where appropriate, other additives. 11. The method according to claim 10, characterized in that the Preparation of one-component adhesive systems homogenization the components are carried out in the absence of oxygen. 12. The method according to claim 10, characterized in that one for Preparation of two-component adhesive systems of the polymeri sible compound or compounds only one component of the Activator system admits and the second component of the activator Only when using the adhesive system alone or in the Mixture with a further proportion of polymerizable compound or the compounds. 13. Use of the composition according to one or more of Claims 1 to 9 as - in particular aerobic - hardening sealing and adhesive system, spreadable for the Surface coating, molding compound or as an additive to inks and Printing inks. 14. adhesive composition comprising in addition to activators and ge if appropriate further customary additives one or more Ver compounds as defined in claims 1 to 9.